Method for coalescing a dispersed aqueous caustic phase from a stream of hydrocarbons



US. Cl. 252324 4 Claims ABSTRACT OF THE DISCLOSURE An aqueous caustic dispersed in a stream of hydrocarbons is coalesced by passing the stream over silica sand having grains of an angularity between from 0.1 to 0.6 Krumbein roundness factor and an ASTM standard sieve size range between the larger and the smaller-sized particles of less than about holes per lineal inch, said sieve size range also being within the broad range of about ASTM No. 10 sieve size to about ASTM No. 100 sieve size. From to 100 parts of water per 1,000,000- parts of hydrocarbons are introduced into the stream before it passes over the sand. This water washes the sand free of any caustic entrained by the sand.

This invention relates to an improved method of coalescing dispersed aqueous phases from hydrocarbon streams and more particularly to the use of silica sand of a particular angularity and size as the coalescing medium.

Water-washing followed by a settling period was used to remove entrained treating solutions from fuels prior to the introduction of rock salt coalescers. Their use has resulted in a considerable reduction in investment costs and in fewer problems with hazy fuels. However, carryover of treating solutions and brine from the coalescers has been a recurrent problem. The introduction of brine and caustic solutions into tanks decreases the effectiveness of anti-rusts and other additives, which are added to fuels, and furthermore many complaints of slugged filters by customers of the petroleum industry can be traced to treating solution carry-over.

Materials, other than NaCl, can be used or have been proposed for use as coalescing media. Uses of blast furnace slag coated with water glass, sand towers, glass Wool, molecular sieves, air coalescing, fluidized droplet beds, porous polyethylene, and excelsior have either been used or proposed for use; however, their effectiveness has not been demonstrated. Sand towers, for instance, are not new to the petroleum industry but they are not commonly used because of pressure drops and repeated low efficiency.

Also, one of the problems encountered using NaCl coalescers is that brine, which greatly accelerates the corrosion of steel, can be introduced into storage tanks. Also, certain fuels seem to be inherently more corrosive than others; for example, virgin gas oil. Therefore, an ideal coalescing medium would be one which would give a non-corrosive aqueous solution or no aqueous phase, and which would reduce the inherent corrosivity of the fuel being coalesced.

The problem, for example, of removing caustic hazes is particularly accentuated by attempting the removal by the use of a medium other than salt. It is desirable, therefore, to provide a coalescing medium which would be equal to or surpass the effectiveness of salt and yet overcome its deleterious effects. The medium to be effective should be relatively insoluble in both hydrocarbon and treating solution to avoid the corrosion problems which are encountered using water soluble materials.

3,445,399 Patented May 20, 1969 Secondly, the coalescing medium should also be inert with respect to water and oil to prevent the formation of reaction products, which could cause excessive pressure drop in the coalescing bed, or could carry out and cause difficulty elsewhere. Thirdly, the medium should be comparable in cost to NaCl.

It has been discovered that silica sand of particular angularity and size makes a most effective coalescing medium in removing dispersed aqueous phases from hydrocarbon streams and in particular a most effective medium in removing caustic hazes from these streams.

Accordingly, an important object of this invention is to provide a coalescing medium that will effectively and efficiently remove dispersed aqueous phases, including, but not limited to, caustic hazes from hydrocarbon streams, thereby producing a clear and bright efiluent.

Another object of this invention is to provide a co alescing medium which will allow the attainment of greater linear velocities through the medium, thus making it possible to reduce the size of coalescing vessels.

A further object of this invention is to provide a coalescing medium which is not corrosive to tanks and equipment and one whose presence will be eliminated from finished products.

A still further object of this invention is to provide a means to overcome the deleterious effects caused by pressure drop across the coalescing medium.

Other objects of the invention will become apparent to one skilled in the art upon consideration of the accompanying disclosure.

Briefly stated, this invention provides a method for coalescing a dispersed aqueous from a hydrocarbon stream by passing the stream downward through a contacting mass of silica sand having an approximate angularity range of between about 0.1 to 0.6 Krumbein and an approximate sieve size range of about ASTM Standard No. 10 sieve to about No. 40 sie've. This invention also provides for a method in overcoming pressure drop across the contacting mass by introducing a liquid, immiscible in the hydrocarbons and miscible in the dispersed phase, into the hydrocarbon stream prior to its passing downward through the contacting mass thereby allowing the coalesced phase to freely drain from the contacting mass.

Silica sand of the angularity and particle size mentioned above has been found to be an excellent material for coalescing dispersed phases, particularly caustic hazes. The angularity of the grains provides more exposed contact surfaces for wetting by the phase. Also the angularity tends to cause the stream to pass through the medium in an irregular manner which allows more of the phase to contact the surface of the grains. As the particle size decreases, shallower beds can be used for the same coalescence. It is conceivable that very fine angular silica sands, down to mesh, could be used to fabricate a depth type coalescing element (with walls 2-3 inches thick) that would be etfective in removing caustic hazes in conventional mechanical coalescers of the Warner-Lewis type. To date every attempt to manufacture a cartridge that will satisfactorily coalesce caustic hazes, yet withstand caustic attack over long periods of time, has failed. The optimum angularity range is about a Krumbein factor of 0.4 to 0.6 and the optimum sieve size 20-40 (ASTM Standard Sizes).

As explained above, sand towers have been used for coalescing dispersed phases from hydrocarbon streams and are not new to the petroleum industry. However, they are not widely used because of pressure drop problems and low efiiciency. In order to overcome pressure drop large coarse gravel or round-grain sand are used. When these materials are used, however, the beds must be several feet in thickness in order to provide adequate coalescing.

3 4 The pressure drop across the bed is caused by the fact permits the reduction in size of the tower or vessel is that the viscosity of the caustic phase may be so high that in the use of silica sand linear velocities three times that it cannot drain fast enough from the bed. As a result greater h lt can b achieved, the Space between the Sand Partlcles gradually fills Wlth Silica sand of the type utilized in the method of the incaustic, the pressure differential through the bed increases and coalescing efficiency declines.

In accordance with this invention it has been discovered that this pressure drop may be overcome by continuously EXAMPLE 1 proportioning a fluid, such as water to the oil entering the coalescer to dilute the caustic and lower the vis- A caustic haze was coalesced from a hydrocarbon vention is commercially available.

The following executional examples illustrate the invention:

cosity, thereby permitting the caustic to drain from the stream under downflow conditions in a coalescing vessel. bed. To produce a coalescer eflluent that is clear and The grains of the silica sand used as the contact medium bright, the water addition rate is critical. The optimum were in the optimum range of angularity and sieve size fluid addition rate is in the range of about 50400 parts with 36% voids. The depth of the bed was 11 inches. per million parts of hydrocarbons. If a fluid other than The effluent produced was bright and clear.

Caustic in oil 1 (gms.

Flow conditions Bed equiv. NaOH/liter) Caustic removed Flow Linear Contact 1 Press. Time Cc. caustic rate, Space vel., time, drop, Vol. period, per 1,000 Run No. cc./min. vel. cc./min. min. A p.s.1. Feed Efifl. caustic cc. hrs. liters oil 1 Brom Phenol Blue used for titration indicator. Values reported as equliivalteiit gms. NaOH per liter represent total basicity of oil sample to a p o 2 Space velocity defined as follows: vol. of oil flowing per hour divided by volume of bed.

water is utilized, it is, of course, necessary that the fluid EXAMPLE 2 m cible i h ro this i l i he ggg g p the yd carbons and c b e n t The following results were obtained under the same The method 3 this invention may be employed in any conditions as Example 1 with the exception that the bed coalescing tower or vessel. When employing the method depth was 17 Inches f Water w Introduced Into the in accordance with the invention, it will be possible to hydrocarbon stream 111 the Optlmum range of -100 greatly reduce the size of the tower or vessel used since, P-P- Caustic in oil, Flow conditions Bed mg. NaOH/liter Haze points KF water Con- Oil Water Percent Linear tact Press. Feed Efil. rate, rate, H2O on Space vel., time, drop, Feed, Efil, cc./min. cc./min. oil flow vel. cm./min. min. p.s.1. Feed Efli. Init. Def. Inlt. Def. p.p.m. p.p.m.

1,080 120 11.1 18.4 30. 9 1. 2 4 8.6 1 97 e4 242 1, 530 5.9 26.2 52.2 .s 5 13 6 .2 99 97 210 252 1, 400 so 5. 7 23. 9 47.8 .9 5 10. 0 .2 e3 282 990 110 11. 1 16.9 33.8 1. 3 5 6. 9 .2 105 as 106 103 294 315 1 Based only on oil flow rate. 2 Brom Thymol Blue used for titration indicator. Values obtained at a pH of 7 largely represent quantity of N aOH present in sample.

EXAMPLE 3 for example, a two-foot thick bed of silica sand in the 45 Thi example represents a comparison of results beoptimum ranges of grain angularity and size will produce tween the method of this invention and a conventional an efliuent clearer and brighter than will a sixteen-foot salt tower. The angularity of the silica sand grains Wa bed of quarter inch rock salt. An additional factor which in the optimum range.

DESIGN CONDITIONS: SAND COALESCER VS. SALT TOWER FOR REMOVING HAZE FROM A HYDRO- CARBON STREAM Sand coalescing Sand coalescer Salt tower w/water Wash Flow rate, b./d. 2,000.

Flow rate, bbls./hr. 500 500.

Flow direction Up Down. Vessel size:

Dia., ft 10 8.

Height, ft 10. Coalescing bed:

Material Silica sand.

Particle size, sieve s 2 0.

Void space, percent 36. Cross-sectional area of vessel, sq 50.2. Cross-sectional free area of bed, sq. ft. 18.1. Volume of bed (apparent), cu. ft. 100.

Space velocity, vol. oil/hr./vol. of be 29.4. Linear volocity through bed it./mi.n 2.71. Contact time in bed, min-.. .74. Pressure drop across bed, 6-

7. Temperature of oil in vessel, F. 95-125. Caustic in oil:

Entering vessel, mg. NaOH per liter- 10.

Leaving vessel, mg. NaOH per liter 0.2. Volume of separated phase removed, b./d 600. Properties of hydrocarbon stream:

Gravity, API. 2820.

Sp. grav. at 60 F .88.

Viscosity, cs. at 60 5.1.

Viscosity, cs. at F 2.9. Properties of separated phase, s g a 1.0. Water addition, percent H O in feed 5.

1 Space velocity, vol. of oil H20/hl./V0lof bed. 1 Based 011 Vol. 0! oil -I- water.

6 Having thus described the invention, what is claimed 2. The method defined in claim 1 wherein said sand consists essentially of sand graded within ASTM Standard 1. A method for coalescing a dispersed aqueous caustic and 20 phase from a Stream of hydrocarbons, comprising the 3. 1The method defined 1n cla1m 2 whereln sa1d sand steps of: consists essentlally of sand graded w1th1n ASTM Standard (1) providing a shallow sand bed consisting essentially 5 g i i ggg zggd in claim 3 wherein said sand f Slhcg g g t an gs g z g grains have an angularity between 0.4 and 0.6 Krumbein a out an urn ein roun ess ac or an factoL an ASTM standard sleve size range between the References Cited larger and the smaller-sized particles of less than 10 about 20 holes per lineal inch, said sieve size range UNITED STATES PATENTS also being within the broad range of about ASTM i -5 9 61 52 6 g et -.1" tST .00 emote 0 me to abou A M 1 2,133,186 10/1938 Campbell 252 324 (2) passing said stream through said bed to coalesce 5:55:33 the aqueous caustic phase, whereby a Pressure p 2,838,116 6/1958 Clark et a1. 252-855 x develops across sa1d bed; and 3,011,970 12/1961 Goodman et a1 2081 8 8 (3) substantially reducing said pressure drop by intro- 3,215,619 11/1965 Brooke 208-188 ducing into said stream before passing said stream HERBERT B GUYNN P E through said bed water in the ratio of about to n my xammer' parts of water to 1,000,000 parts of said hydro- X-R- carbons. 208187, 188; 252-330 

